Literature Review


Clathrate hydrates
Gas hydrates are ice-like, solid crystalline non-stoichiometric compound belonging to the clathrate (i.e., inclusion compounds) group. Gas hydrates consist of water molecules that interconnected by hydrogen bonds in a cage like structural lattice. Clathrate hydrates are stable under the high pressure and low temperature. Encapsulation of a hydrophobic guest molecule stabilizes the clathrate structure due to van der Waals force. Since any kind of bonding is absent between guest molecules and host molecules, the guest molecules are able to rotate freely inside clathrate cage. Naturally occurring methane hydrates in marine sediments and below permafrost regions are expected as significant future energy source [1, 2], and recently methane gas hydrate became very important research topic worldwide.


Types and properties of gas hydrate
There are three types of clathrate structures commonly found such as structure I, structure II and structure H [3]. Unit cell of structure I has 46 water molecules consisting two pentagonal dodecahedron (512) cages having 169Å3 volume each and six hexagonal truncated trapezohedron (51262) cages having 216Å3 volume each [4]. The smaller voids can encompass gas molecules of size less than 5.2 Å while the larger molecules can hold gas molecules of size less than 5.9 Å. Unit cell of structure II has 136 water molecules consisting sixteen 512 cages and eight 51264 cages. Unit cell of structure H has 34 water molecules has six fundamental consisting three 512 cages, two 435663 cages, and one 51268 cage. Guest molecules play an important role towards formation of specific types of gas hydrate as well as gas hydrate formation conditions [3, 5]. The amount of guest present inside clathrate is dependent on the external pressure and temperature. Geometrical parameters of clathrate hydrates are summarized in Table 1 and pictorial representation of different clathrate cage structures shown in Figure 1.

06 5.33 3.91 4. the specific volume of water increases by 26-32%. one volume of water enclathrates 207 volumes of methane gas [6]. During transformation to the gas hydrate state. of cavities per clathrate structure Average cavity radius (Å) Coordination no Number of waters per unit cell 20 46 24 20 136 28 20 20 34 36 3.91 4.Table 1: Geometrical parameters of different gas hydrate structures [3] Gas hydrates structure Cavity Description No.95 4. .71 Small 512 2 Large 51262 6 Small 512 16 Large 51264 8 Small Medium 512 3 435663 2 Large 51268 1 SI S II SH In case of methane hydrate.73 3.

Figure 1: Different gas hydrate structures [3]. Formation of gas hydrates . 3.

and if it is a dynamic or static condition [9]. This time delay is caused by [7]:  Rearrangement of hydrate interfaces  Rearrangement throughout the hydrate  Effects of the solid surface . the history of the water. Figure 2: Phase diagram of gas hydrate. al. Heat transport during hydrate formation to remove latent heat of fusion. As a result the induction time is therefore considered a stochastic process. even though the variables in a system are kept constant the induction time may vary. and may take only a few nanoseconds or up to several months. 8].Calculation of change in Gibbs free energy of gas hydrate formation is necessary for analyzing clathrate formation condition [7. pressure and temperature. stated the following conditions for gas hydrate formation [9]: 1. However. and concludes by the appearance of a detectable hydrate volume. water and gas composition. depending on the system. As mentioned. it is a stochastic process. even though increased interface between the two constituents increase the probability of nucleation [7. It has to be thermodynamically favorable (∆G < 0) 2. 10]. Makogon et. the presence of substrate material. cooling rate. Availability of hydrate constituents (water and hydrate former) 3. The induction time starts by the formation of the first crystal nuclei. Experiments have shown that the length of the metastable state of the system (the induction time) is dependent on the apparatus setup.

 For the Heterogeneous nucleation case presence of a hydrate film at the interface between the two phases will also increase the (macroscopic) induction time. Experimental studies as well as thermodynamic and kinetic modeling of gas hydrates nucleation and growth process have been carried out for better understanding of gas hydrate formation process by several researchers [11]. There are two types of inhibitors such as thermodynamic inhibitor and low dosage inhibitor. So inhibition is very necessary. makes liquid water more stable than hydrate water. Unscheduled formation of gas hydrates in oil and gas pipelines is a great concern to flow assurance till date. Inhibitors and inhibition of gas hydrates Flow assurance in production and transportation pipelines is the main reason for previous extensive hydrate research by several petroleum companies. Figure 3: Phase diagram of gas hydrate showing gas hydrate decomposition. ethanol. 4. and salt. The effect of the inhibitor is both through the dilution of water and through the impact of the inhibitor on the water activity. since it reduces . etc. Thermodynamic inhibitors shift the hydrate P-T curve by changing the thermodynamic properties of the system. Addition of thermodynamic inhibitors like methanol.

KCl. alcohols and water soluble salts are examples of thermodynamic inhibitors. estimates the phase equilibria conditions of natural gas hydrates in the presence of methanol. The mechanism of hydrate inhibition is that the inhibitor mainly dissolves in the free water phase thereby reducing the fugacity of water. Non toxic polymers are usually kinetic gas hydrates inhibitors [12. al.g.. Masoudi et.g. mono ethylene glycol and methanol) used for gas hydrate prevention scenarios in the gas and oil industry [17]. 15]. Lee et. 12]. reducing the fugacity of water also reduces the tendency of hydrates to form [13. Generally polar compounds such as glycols. NaCl. Brief illustration of different gas hydrate inhibitors  Methanol Methanol (CH3OH) is long known as thermodynamic gas hydrate inhibitors. Ethylene Glycol    . CaCl2) and hydrate organic inhibitors (e.. 5. ethylene glycol. al. which lowers the activity of the water and shifts the equilibrium lines for hydrate formation in the phase diagram to lower temperatures like classical antifreeze [18 . Methanol is good inhibitor to gas hydrate formation because it is easily vaporized into the gas phase [21] and it has a lower viscosity and surface tension as a function of temperature [22]. But methanol has some drawbacks such as it is flammable and toxic [21]. and NaCl aqueous solutions [16]. As water is the principal component of gas hydrates.the chemical potential of aqueous water [8. developed thermodynamic model to obtain better understanding of gas hydrate inhibition effects of combinations of salts (e. al. Bullin et. 14]. design optimum usage of methanol for hydrate inhibition in a gas gathering system suggesting condensing and removing as much water as possible prior to injecting methanol . considering safety factors and seasonal adjustments [23]. Low dosage hydrate inhibitors have two varieties namely kinetic inhibitors and anti-agglomerates.20].

02 wt. critical micellar concentration (CMC) and stability of methanehydrate was studied by Moraveji et. Experimental Study of gas hydrates The gas hydrate inhibiting properties of different chemical additives have been studied using high-pressure test wheel for flow simulation experiment by Urdahl et al(1995) [21].99 mol%) in a quiescent system.17% of propane) hydrate formation with an anionic surfactant (linear alkyl benzene sulfonic been industrialized due to slow formation rate and the acid) [18] . % of Poly N-vinylcaprolactam (PVCap) separately and subsequently done Raman and NMR spectroscopic measurements formed clathrate hydrates found the evidence of methane transformation to the hydrate phase from Time-wise Raman data [22]. A critical micellar concentration (CMC) best determined by hydrate induction time and the strong positive effect of surfactant like micellar solution containing sodium dodecyl sulfate on gas hydrates formation rates has been indentified experimentally by Zhong et al(2000) [24].A water-surfactant-gas system can be used as stabilizer of gas hydrates. The effect of sodium dodecyl sulfate (SDS) as an anionic surfactant on the thermodynamics.96 mol%. ethane 4. that methanol can also act as a kinetic promoter for formation of gas hydrates [16]. Karaaslan et al. considered the methane and gas mixture (with 88. propane 2. formation 6. Sun et al. showed that the micellar surfactant solutions are effective promoter [19]. They observed that the effect of an anionic surfactant (sodium dodecyl sulfate) on natural gas storage in hydrates is more pronounced compared to the effect of a nonionic surfactant (dodecyl polysaccharide glycoside) [19]. Sun et.05 mol%. Subramanian et al (1999) carried out experiments with the methane hydrate forming system with de-ionized water. It was experimentally found by Lee et al (2007) that the addition of starch and PEO influenced the hydrate formation induction time such a way that the hydrate memory is . reported that SDS is the best surfactant for promoting methane hydrate formation [17]. The formation of structure II (S II) from binary gas mixtures of methane (CH4) and ethane (C2H6) for specific compositions is identified through Raman and NMR spectroscopic measurements by Subramanian et al (2000) [23]. formation rate. a nonionic surfactant. and 0. their mixtures and cyclo-pentane for improving the hydrate formation of a synthetic natural gas (methane 92. Link et al. al [20]. It is found by Bobev et. al. studied the application of an anionic surfactant.

developed a general kinetic model of hydrate formation using both phase field and molecular dynamics simulation that can be used to optimize technologies for the exploitation of hydrate reservoirs [30]. It is found that the exact location of this transition is a function of pressure and of cluster size [29]. NMR. A two-stage computational study is carried out by Kuznetsova et. n=4–21. Methane. to simulate initial clathrate hydrate formation[35]. al. It is also found that the accuracy of the PMF depends on the water–water. Jiang et. water–methane and methane–methane interaction potentials used [28]. Global cluster structure optimization of CH4 (H2O)n. provide comparison syudy of the properties of Xenon. in aqueous solutions under various conditions [31]. Saman Alavi et. Gas hydrate nanoclusters surrounded by water shells are studied using the molecular dynamic method by Brodskaya . did Moleculardynamics study of structure II hydrogen clathrates and found that Double occupancy in the small cages increases the energy of the structures and causes tetragonal distortion in the unit cell [32]. for polyvinylpyrrolidone (PVP) and polyvinylcaprolactam (PVCap). and the combined effect of pressure and the presence of a methane molecule on structural transition of water cluster are studied by Hartke (2009) .et. also carried out Molecular dynamics simulations of binary structure H hydrogen and methyl-tert-butylether clathrate hydrates [33]. and Raman spectroscopy characterization that the large cages are almost fully occupied by a combination of all three gases and the small cages were about 90% occupied by methane [26].al. Saman Alavi. It is found by Rajnish Kumar et al (2008) after studying the growth of gas hydrate through powder X-ray diffraction (PXRD). and Carbon Dioxide Hydrates from Equilibrium and Nonequilibrium Molecular Dynamics Simulations [34]. 7. al. Molecular simulation study of gas hydrates Molecular dynamics has potential application to simulate and study promoters and inhibitors for gas-hydrates in different conditions. The potential of mean force (PMF) between a dodecahedral water cage (DWC) and dissolved methane are obtained by Guo et al (2009) by using the method of constrained MD simulations. Large-scale nanosecond classical molecular dynamics calculations have been employed by Tse et. Kvamme et. al. It is found by Chongwei Xiao et al (2010) that EMIM-Cl is the most effective thermodynamic inhibitor after investigating six dialkylimidazolium halide ionic liquids for their potential application as novel gas hydrate inhibitors [27]. al.suppressed [25]. al.

Spectroscopic study and Ab initio calculation based study of gas hydrates Cage occupancy analysis and hydration number calculation from Raman spectroscopy [39. Phase equilibrium condition for methane hydrate formation and phase equilibria calculations for methane hydrate in various aqueous solution systems have been reported [50-53]. Classical molecular dynamics simulations of clathrate-methane-water and an inhibitor of clathrate formation are performed using different inhibitor/water ratios and a hydrate system modeled as a 51262 cavity [38]. Geometry optimization of (H2O)20H+ and (H2O)21H+ clusters by HF/6-31G* level followed by a single-point energy calculation at the MP2/6-31G* level are carried out by Khan [54]. The stretching vibrations of methane in the small and large cavity of structure I clathrate hydrate have been studied by Tse using ab initio molecular dynamics using a linear scaling pseudo potential density functional method [37]. They found that the presence of AATA in the vicinity of the water cavities leads to its deformation and the elongation of the hydrogen bonds responsible for keeping the dodecahedral (H2O)20 together. [57] after performing geometry optimization of do-decahedron water cluster cavities (512 and 435663) with CH4. [55]. 46] and molecular dynamics [47-49] have been carried out. Formation process of gas hydrates as well as stability analysis of clathrate in different conditions through experimental study [42-44]. 8. [56] using DFT. al. which corresponds to the melting point of bulk crystal upon the use of the SPC/E water model [36]. The role of antifreeze glycoprotein as inhibitor of clathrate-hydrate formation and the effect of AATA peptide are simulated and studied by Cruz-Torres et. al. They reported that the melting of ice cluster is observed at 215 K. al. thermodynamic modeling [ CO2 and N2 guest molecules using the Hatree–Fock (HF) level of theory with the 6- .40]. It is concluded by Lebsir et. C2H6. identification of guest molecule and vibrational behavior of guest molecule in clathrate cages through IR spectroscopy analysis [41] have been reported.Study of clathrate and different water cluster systems by ab-initio methods has become significantly important. al. Gualdro´n et.Geometry optimization of representative isomers of various dodecahedral and tetra-kai-decahedral buck ball water cluster with or without guest molecule by first principle method have been carried out by Chihaia et. al.

31G (d) basis set. There is no ab initio study on the stability of gas-hydrate in presence of cations/anions. Molecular structure of gas hydrates at various operating conditions (in presence of (Na+. The accommodation of hydrogen in different clathrate cages and stability of clathrate hydrates+nH2 systems are studied by Chattarajet. . which are expensive and time-consuming: Computation studies are valuable tools to elucidate promoters/inhibitors action mechanism at the atomistic scale and help in better scientific understanding. [58].al.ions) and effect of addition of chemical reagents for stabilizing and de-stabilizing the gas hydrates are significant for gas hydrates exploration and recovery. Methane hydrate containing 19-25 water molecules is revealed to be the most stable clusters among optimized bi-cavital (CH4)2-(H2O)n cluster structures using DFT theory by Terleczky et. Scope of research Promoters and inhibitors for gas-hydrates are selected by trial and error experiments. Cl. K+. that the guest molecules provide a better stabilization for the irregular dodecahedron cage structure. 9. al. using DFT and MP2 methods [59].